WO2006025709A1 - Catalyseur metallocene sur support, procede de preparation dudit catalyseur et procede de preparation de polyolefine utilisant ledit catalyseur - Google Patents

Catalyseur metallocene sur support, procede de preparation dudit catalyseur et procede de preparation de polyolefine utilisant ledit catalyseur Download PDF

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WO2006025709A1
WO2006025709A1 PCT/KR2005/002913 KR2005002913W WO2006025709A1 WO 2006025709 A1 WO2006025709 A1 WO 2006025709A1 KR 2005002913 W KR2005002913 W KR 2005002913W WO 2006025709 A1 WO2006025709 A1 WO 2006025709A1
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radical
compound
supported
metallocene catalyst
carrier
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PCT/KR2005/002913
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English (en)
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Eun-Jung Lee
Ki-Soo Lee
Sangwoo Lee
Seungwhan Jung
Jong-Joo Ha
Choong-Hoon Lee
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Lg Chem. Ltd.
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Priority to EP05808515.0A priority Critical patent/EP1784431B1/fr
Priority to CN2005800020593A priority patent/CN1910207B/zh
Priority to JP2006549157A priority patent/JP4652343B2/ja
Publication of WO2006025709A1 publication Critical patent/WO2006025709A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/02—Carriers therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0261—Complexes comprising ligands with non-tetrahedral chirality
    • B01J2531/0263—Planar chiral ligands, e.g. derived from donor-substituted paracyclophanes and metallocenes or from substituted arenes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/46—Titanium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/48—Zirconium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65925—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually non-bridged
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged

Definitions

  • the present invention relates to a supported metallocene catalyst, and more par ⁇ ticularly to, a supported metallocene catalyst which does not easily separate from a carrier, a method of preparing the catalyst, and a method of preparing a polyolefin using the catalyst.
  • Metallocene catalysts have a uniform distribution of active sites, and thus, when using them in the production of a polymer, the distribution of molecular weight of the polymer obtained is narrow, the copolymerization of the polymer can be easily performed, and the distribution of a second monomer is uniform. Further, when using metallocene catalyst s in the polymerization of propylene, a stereostructure of the polymer can be controlled according to the symmetricity of a catalyst.
  • Ziegler- Natta catalyst s When Ziegler- Natta catalyst s are used, only isotactic polypropylene can be prepared, but when metallocene catalyst s are used, various polypropylenes, for example, isotatic, syn- diotactic, atactic, and hemiisotactic polypropylenes, can be stereoregularly prepared.
  • syndiotactic polypropylene synthesized using a metallocene has low crystallinity, appropriate rigidity and hardness, and high transparency and impact resistance. That is, when the metallocene catalysts are used in the preparation of polyolefins, conformation of the polyolefins can be controlled and physical properties of the polymers can be easily controlled. Thus, vigorous research has been conducted on metallocene catalysts.
  • the technique of olefin polymerization using a homogeneous catalyst cannot be used in a gas phase process or a slurry process, since the shape of the polymer cannot be easily controlled. Further, an excess amount of MAO is required to maximize the activity of the metallocene catalyst.
  • the metallocene catalyst should be supported on an appropriate carrier. The supported metallocene catalyst can control the shape of the obtained polymer and control the molecular weight distribution according to its applications. Further, the supported metallocene catalyst can increase an apparent density of the obtained polymer and reduce fouling in the reactor.
  • conventional methods of preparing a supported metallocene catalyst include a method including chemically and physically binding a metallocene compound to a carrier and then contacting the resultant product to aluminoxane, a method including supporting aluminoxane on a carrier and then reacting the resultant product with a metallocene compound, a method of contacting a metallocene compound with aluminoxane and then supporting the resultant product on a carrier, etc.
  • the supported catalyst should maintain a single active site structure after being supported. In order to prevent the reactor fouling, the catalyst must not be separated from the carrier during the polymerization.
  • the particle size, particle size distribution, and apparent density of the polymer depend on the particle shape and the mechanical properties of the supported catalyst.
  • Korean Laid-Open Patent Publication No. 10-0404780 describes a metallocene compound having a silacycloalkyl substituent and a supported catalyst using the compound.
  • the supported catalyst is used in a gas phase process or a slurry process, the catalyst is separated from the carrier, and thus, may induce reactor fouling.
  • Japanese Laid-Open Patent Publication No. Hei 6-56928 describes a method of preparing a supported metallocene catalyst, including supporting a ligand on a surface of a carrier via a chemical bond and then, binding metal to the ligand. This method is very complicated and a large amount of the catalyst cannot be easily supported on the carrier.
  • the method including supporting aluminoxane on a carrier and then reacting the resultant product with a metallocene compound among the above methods is the oldest method of preparing a heterogeneous catalyst having a single active site.
  • silica can be reacted with a solution of aluminoxane and filtered to obtain a filtrate and the filtrate can be reacted with zirconocene dissolved in toluene or an aliphatic hy ⁇ drocarbon solvent, thereby preparing a supported catalyst.
  • the obtained supported catalyst can be directly used in the polymerization or copolymerization of ethylene performed in a gas phase process or a slurry process.
  • the cocatalyst is physically/chemically secured on a surface of the carrier and the catalyst forms an ion bond with the cocatalyst like a homogeneous catalyst, and thus, the catalytic activity is relatively high.
  • this method can be easily applied in a conventional gas phase or slurry process. However, separation of the catalyst from the carrier cannot be completely prevented, and thus reactor fouling can occur. Also, the amount of aluminoxane that can be bound to silica is limited, and thus, the amount of the metallocene compound that can be bound to aluminoxane is limited. Disclosure of Invention
  • the present invention provides a supported metallocene catalyst which is not separated from a carrier when polymerizing olefins, thus preventing reactor fouling, and has high polymerization activity.
  • the present invention also provides a method of preparing the supported metallocene catalyst.
  • the present invention also provides a method of preparing a polyolefin using the supported metallocene catalyst.
  • a supported metallocene catalyst comprising:
  • C and C are each independently selected from the group consisting of cy-
  • R m and R n are each independently a hydrogen radical or a C -C alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl, arylalkenyl or alkylsilyl radical;
  • R and R are each independently a hydrogen radical or a C -C hydrocarbyl radical;
  • each of a, a', b, and b' is an integer ranging from 1 to 4.
  • M is a transition metal of group 4B, 5B or 6B of the periodic table
  • Q is a halogen radical or a C -C alkyl, alkenyl, aryl, alkylaryl, arylalkyl radical; or a C -C alkylidene radical;
  • [28] z is 0 or 1, and if k is 3, z is 0;
  • B is a radical selected from the group consisting of a C -C alkyl radical and a hy ⁇ drocarbyl radical containing silicon, germanium, phosphor, nitrogen, boron, or aluminum;
  • J is a radical selected from the group consisting of NR S , O, PR S , and
  • R s is a C -C alkyl radical or a substituted alkyl radical ;
  • Z is an oxygen atom or a sulfur atom
  • R and R' are each independently a hydrogen radical, a C -C alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl radical, or an arylalkenyl radical, and the two R' may be linked together to form a ring;
  • G is a C -C alkoxy, aryloxy, alkylthio, arylthio, phenyl, or substituted phenyl, and may be linked to R' to form a ring;
  • G is alkylthio, arylthio, phenyl, or substituted phenyl, Z is an oxygen atom;
  • Z' is an oxygen atom or a sulfur atom, and at least one of the two Z' is an oxygen atom; and
  • R and R' are each independently a hydrogen radical or a C -C alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl, or arylalkenyl radical, and R and R' or the two R' may be linked together to form a ring;
  • Z' is an oxygen atom, a sulfur atom, a nitrogen atom, a phosphor atom, or an arsenic atom
  • R'" is a hydrogen radical, a C -C alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl, or arylalkenyl radical, and the R'" radicals are identical or different from each other
  • R"" is a hydrogen radical, a C -C alkyl, aryl, alkenyl, alkylaryl, alkylsilyl,
  • n 1 40 arylsilyl, phenyl, or a substituted phenyl radical; and [48] n is 1 or 2, and if Z' is oxygen or sulfur, n is 1, and if Z' is nitrogen, phosphor, or arsenic, n is 2. [49] According to another aspect of the present invention, there is provided a method of preparing a supported metallocene catalyst, comprising:
  • a method of preparing a polyolefin comprising polymerizing an olefin monomer at 50-150 0 C in the presence of the supported metallocene catalyst.
  • a Lewis acid-base interaction occurs between the metallocene catalyst and a cocatalyst, and thus a larger amount of metallocene can be supported on a carrier. Also, little catalyst is separated from the carrier during the polymerization of polyolefin in a slurry or gas phase method, thereby preventing fouling , i.e., the ac ⁇ cumulation of the polymer on walls of the reactor or aggregation between the polymer particles, and the polymer prepared has a good particle shape and a high apparent density.
  • the supported metallocene catalyst can be suitably used in a con ⁇ ventional slurry or gas phase polymerization process.
  • the physical properties and molecular weight distribution of the polyolefin can be controlled over a wide range and may be molded in various products, for example, rotary molded products, injection molded products, films, containers, pipes, and fibers.
  • the molecular weight distribution can be controlled in a single reactor with low production costs.
  • a Lewis acid-base interaction occurs between a functional group of a metallocene catalyst and a cocatalyst, thus increasing the amount of metallocene that can be supported on a carrier.
  • the metallocene compound is more strongly bound to the cocatalyst due to the Lewis acid-base interaction, in addition to an ionic bond between the metallocene catalyst and the cocatalyst, and thus, the metallocene compound of a supported catalyst is not separated from the carrier during the poly ⁇ merization of the olefins, thereby preventing fouling.
  • M may be titanium, zirconium, or hafnium and Q may be halogen, preferably chlorine.
  • B is a structural bridge between C and C
  • R 1 a R m b is selected such that (C p R 1 a R m b ) is differently substituted from (C p 1 R 2 a 1 R
  • metallocene compound having Formula 2 include [A-O-(CH ) -C H ] C(CH ) [C H ]ZrCl [A-O-(CH ) -C H ]Si(CH ) [C H ]ZrCl , [C H JC(CH"
  • V V 2 a 13 8 2 5 5 3 2 a 13 8 2 an integer from 4 to 8 and A is a radical selected from the group consisting of methoxymethyl, t-buthoxymethyl, tetrahydropyranyl, tetrahydrofuranyl, 1-ethoxyethyl, 1 -methyl- 1-methoxyethyl, and t-butyl.
  • metallocene compound having Formula 3 include [(A'-D-(CH ) )](CH )X(C 5 Me4 XNCMe 3 )] TiCl 2 and [(A-D-(CH 2 )a )](CH3 )X(C 5 Me4 )(NCMe 3 )] ZrCl 2 * where a is an integer from 4 to 8, X is methylene, ethylene, or silicon, D is an oxygen atom or a nitrogen atom, and A' is a radical selected from the group consisting of a hydrogen atom, C -C alkyl, alkenyl, aryl, alkylaryl, arylalkyl, alkylsilyl, arylsilyl, methoxymethyl, t-buthoxymethyl, tetrahydropyranyl, tetrahydrofuranyl, 1-ethoxyethyl, 1 -
  • metallocene compound a ccording to embodiments of the present invention include, but are not limited to, the following compounds:
  • A, a, and D are as defined in Formulae 1 through 3.
  • the carrier used in embodiments of the present invention contains highly reactive hydroxy and siloxane groups on its surface since moisture is removed from its surface by drying.
  • Specific examples of the carrier include silica, silica-alumina, and silica- magnesia dried at a high temperature.
  • the carrier may contain oxides, carbonates, sulfates, nitrates, such as Na O, K CO , BaSO , and Mg(NO ) .
  • the drying temperature may be 200-800 0 C , preferably 300-600 0 C , more preferably 300-400 0 C . If the drying temperature is lower than 200 0 C , a large amount of moisture remains on the surface of the carrier, which reacts with the cocatalyst . If the drying temperature is higher than 800 0 C , many hydroxy groups are lost and only siloxane groups remain on the surface of the carrier, and thus, the number of reaction sites for reacting with the cocatalyst is reduced.
  • the concentration of the hydroxy group on the surface of the carrier may be 0.1- 10 mmol/g, preferably 0.5-1 mmol/g.
  • the amount of the hydroxy group on the surface of the carrier may be controlled by varying the conditions when preparing the carrier or the drying conditions of the carrier (for example, temperature, time, vacuum drying or spray drying, etc.).
  • concentration of the hydroxy group on the surface of the carrier is greater than 10 mmol/g, it is likely that the high concentration is induced by moisture, in addition to the hydroxy group on the surface of the silica particle which is impreferable.
  • the dried carrier may be mixed with a cocatalyst having Formula 7 to obtain the carrier on which the cocatalyst is supported.
  • the cocatalyst is a group 13 metal- containing organic metal compound, which is a cocatalyst that is used in the poly ⁇ merization of olefins in the presence of a conventional metallocene catalyst.
  • a bond is formed between the hydroxy group on the carrier and the group 13 metal of the cocatalyst.
  • R is a halogen radical, a C -C hydrocarbyl radical, or a C -C hydrocarbyl radical substituted by a halogen, and the R radicals are identical or different from each other
  • n is an integer equal to or greater than 2.
  • the compound having Formula 7 may be linear, circular, or netlike. Examples of the compound having Formula 7 include methylaluminoxane (MAO), ethyla- luminoxane, isobutylaluminoxane, butylaluminoxane, etc.
  • a molar ratio of [ group 13 metal ]/[transition metal] in the supported metallocene catalyst may be 1-10,000, preferably 1-1,000, more preferably 10-100. If the molar ratio is less than 1, little catalytically active species is formed due to a very small amount of Al, and thus the catalytic activity is very low. If the molar ratio is greater than 10,000, MAO may function as a catalytic poison.
  • the supported metallocene catalyst a ccording to an embodiment of the present invention may be prepared by supporting a mixture of two or three of the compounds having Formula 1 through 3. By using the mixture, physical properties and a molecular weight distribution of the polyolefin to be produced can be easily controlled.
  • the supported metallocene catalyst in itself may be used in the polymerization of olefins by itself. Separately, the supported metallocene catalyst is allowed to contact an olefin monomer such as ethylene, propylene, 1-butene, 1-hexene, and 1-octene, to obtain a prepolymerized catalyst , which may be used in the polymerization of olefins.
  • an olefin monomer such as ethylene, propylene, 1-butene, 1-hexene, and 1-octene
  • a method of preparing a supported metallocene catalyst comprises:
  • the cocatalyst comprising the group 13 metal- containing organic compound is reacted with the carrier containing a hydroxy group on its surface, and then, the metallocene compound having cyclopentadiene, a cy- clopentadiene derivative, or a bridge group substituted with a functional group that is an O-donor and can function as a Lewis base, for example, an alkoxy group, is reacted with the cocatalyst to prepare the supported metallocene catalyst.
  • a Lewis acid- base interaction occurs between the functional group of the metallocene catalyst and Al, and thus, an increased amount of metallocene can be supported on a carrier.
  • the metallocene catalyst having the functional group is more strongly bound to the cocatalyst than a metallocene catalyst which does not have the functional group and forms only an ionic bond with the cocatalyst.
  • the supported catalyst is not separated from the carrier during the polymerization of the olefins, thereby preventing reaction fouling and increasing polymerization activity.
  • the reaction of the cocatalyst with the carrier can be performed in the presence or absence of a solvent.
  • a solvent examples include an aliphatic hy ⁇ drocarbon solvent, such as hexane and pentane, and an aromatic hydrocarbon solvent, such as toluene.
  • the reaction temperature may be - 20-100 0 C , since the reaction solvent is in a liquid phase in this range.
  • the reaction temperature is preferably - 10-60 0 C , and more preferably 0-40 0 C , since the reaction can optimally proceed in this range.
  • the reaction time may be from 10 minutes to 24 hours.
  • the carrier on which the cocatalyst is supported obtained in this way, can be used for the subsequent process, after the solvent is removed under reduced pressure or filtration.
  • the carrier on which the cocatalyst is supported may be subjected to soxhlet filtration using aromatic hy ⁇ drocarbon such as toluene, and then used for the subsequent process.
  • Examples of the solvent that can be used in the reaction of the metallocene catalyst with the carrier on which the cocatalyst is supported include an aliphatic hydrocarbon solvent, such as hexane or pentane, an aromatic hydrocarbon solvent, such as toluene or benzene, a chlorine-substituted hydrocarbon solvent, such as dichloromethane, an ether solvent, such as diethyl ether or THF, and other oraganic solvents, such as acetone and ethyl acetate.
  • the solvent is hexane, heptane, or toluene.
  • the reaction temperature may be 0-100 0 C and the reaction time may be from 5 minutes to 24 hours.
  • the supported metallocene catalyst obtained in this way can be used after the solvent is removed under reduced pressure or filtration.
  • the supported metallocene catalyst may be subjected to soxhlet filtration using aromatic hydrocarbon such as toluene before being used.
  • the polyolefin polymerization using the supported metallocene catalyst according to an embodiment of the present invention may be performed using a solution process, a slurry process, a gas phase process, or a combination of the slurry process and the gas phase process, preferably a slurry process or a gas phase process.
  • a slurry form of the supported metallocene catalyst may be injected into an olefin monomer for polymerization.
  • a slurry is obtained by diluting the supported metallocene catalyst with a C -C aliphatic hydrocarbon solvent which is suitable for the polymerization of olefins, such as pentane, hexane, heptane, nonane, decane, and isomers thereof, an aromatic hydrocarbon solvent, such as toluene and benzene, or a chlorine-substituted hydrocarbon solvent, such as dichloromethane and chlorobenzene, etc.
  • Small amounts of water, air, etc. which function as catalytic poisons may be removed from the solvent by treating the solvent with a small amount of alkyl aluminum, and a cocatalyst may be further used to remove the catalytic poisons.
  • Examples of the olefin monomer to be polymerized using the supported metallocene catalyst include ethylene, propylene, a -olefin, cyclic olefin, etc. and diene olefin monomer and triene olefin monomer which have at least two double bonds.
  • Examples of the monomer includes ethylene, propylene, 1-butene, 1-pentene, 4-methyl-l-pentene, 1-hexene, 1-heptene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-icosene, norbornene, norbornadiene, ethylide- nenorbornene, vinylnorbornene, dicyclopentadiene, 1,4-butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, a -methylstyrene, divinylbenzene, 3-chloromethylstyrene, etc. Two or more of these monomer may be combined for copoly merization .
  • o rganic reagents and solvents required for the preparation of a catalyst and polymerization were obtained from Aldrich and purified using standard methods.
  • Ethylene was obtained from Applied Gas Technology as a high purity product and filtered to remove moisture and oxygen before polymerization. Catalyst synthesis, supporting and polymerization were carried out in isolation from air and moisture to ensure experimental reproducibility.
  • the molecular weight distribution (polydispersity index (PDI)) was calculated by dividing the weight average molecular weight by the number average molecular weight
  • condition E and F 190 0 C .
  • the MI measured in the condition E was designated I
  • the MI measured in the condition F was designated I .
  • the MI value measured under a load of 5 kg in the same conditions as E and F was designated I .
  • Tm melting point
  • ITS. 1 4. 2. 2. 2.
  • the resultant product (4.06 g, 18.9 mmol) was dissolved in 20 D of THF, and then solid n-butyl lithium (1.6 M hexane solution, 11.4 ml) was added to the obtained solution at -78°C without contacting air.
  • the resultant product was warmed to room temperature and stirred for 2 hours, and then all the volatile materials were removed from the product using a vacuum pump and 20 D of THF was added thereto.
  • Zirconium(IV) chloride tetrahydrofuran complex (3.6 g, 9.5 mmole) was added to the resultant product and stirred at 50 0 C for 12 hours, and then all the volatile materials were removed from the product using a vacuum pump.
  • the resultant product was recrystallized with hexane to obtain a white solid (yield 90%).
  • a supported metallocene catalyst was prepared in the same manner as in Example l-(2), except that the metallocene compound obtained in Example 2-(l) (Compound B) was used instead of the metallocene compound obtained in Example 1-(1) (Compound A) .
  • a supported metallocene catalyst was prepared in the same manner as in Example l-(2), except that the metallocene compound obtained in Example 3-(l) (Compound C) was used instead of the metallocene compound obtained in Example 1-(1) (Compound A).
  • 6-methyl-6-t-buthoxyhexylfulvene (6.5 g, 0.026 mol) in THF (50 D ) at -78°C, and then, the mixture was stirred for 12 hours. Subsequently, a saturated NH Cl/water solution and ether were added to the obtained solution to extract the organic layer, and then, a ligand ( 1 Bu-O-(CH ) )(CH )C(C H )(9-C H ) was obtained by chromatography (yield 97%).
  • a supported metallocene catalyst was prepared in the same manner as in Example l-(2), except that the metallocene compound obtained in Example 4-(l) (Compound D) was used instead of the metallocene compound obtained in Example 1-(1) (Compound A).
  • a supported metallocene catalyst was prepared in the same manner as in Example l-(2) (Compound E), except that the metallocene compound obtained in Example 5-(l) was used instead of the metallocene compound obtained in Example 1-(1) (Compound A).
  • 1,2,3,4-tetramethylcyclopentadiene (5 g, 0.041 mol) in 100 ml of THF at -78°C and the mixture was stirred for 2 hours. Then, the solvent was removed and the resultant product was washed with hexane and dried to obtain tetramethylcyclopentadienyl lithium (yield 76%).
  • a supported metallocene catalyst was prepared in the same manner as in Example l-(2), except that the metallocene compound obtained in Example 6-(l) (Compound F) was used instead of the metallocene compound obtained in Example 1-(1) (Compound A).
  • a supported metallocene catalyst was prepared in the same manner as in Example
  • Example 7 except that the metallocene compound (Compound F) obtained in Example 6-(l) was used for the reaction after instead of the metallocene compound (Compound A) obtained in Example 1-(1) had been supported.
  • Each of the supported catalyst s obtained in Examples 1 through 8 was quantified, placed into a 50 D glass bottle, sealed using a rubber film in a dry box, and then removed from the dry box. Polymerization was performed in a 2 £ high pressure reactor equipped with a mechanical stirrer and temperature-controlled. 1 £ of hexane containing 1.0 mmol of triethylaluminum and each of the supported catalysts were charged into the 2 £ high pressure reactor without contacting air and polymerization was performed at 80 0 C for 1 hour while continuously feeding gaseous ethylene monomer at a pressure of 9 kgf/cm into the reactor. The polymerization reaction was stopped by evacuating the unreacted ethylene after stopping the stirring.
  • the obtained product was filtered to remove most of the polymerization solvent and dried in a vacuum oven at 80 0 C for 4 hours.
  • the ethylene polymerization activity, the molecular weight and molecular weight distribution, the melt index, and the melting point of the polymer obtained using each of the supported catalysts are shown in Table 2.
  • Si[C (CH ) ]NC(CH ) ]TiCl were respectively used as a catalyst .
  • the ethylene poly ⁇ merization activity, the weight average molecular weight, the molecular weight dis ⁇ tribution (PDI), and the melting point of the polyethylene are shown in Table 1.
  • Supported metallocene catalysts were prepared in the same manner as in Example l-( V 2), excep r t that ( V C 6 H 13 -C 5H 4) 2 ZrCl 2, ( V CH 3 ) 2 C( V C 5 H 4 )( V C 13 H 9 )ZrCl 2, ( V CH 3 ) 2 Si[C 5 (CH 3 ) 4 ]
  • Example 9 Compound A, which was used in Comparative Example 1, supported on the carrier was used in Example 9, and the metallocene compound ( C H -C H ) ZrCl , which was used in Comparative Example 7, supported on the carrier was used in Comparative Example 10.
  • the supported metallocene catalyst according to an embodiment of the present invention had a high activity due not only to the high activity of the metallocene compound used in the supported metallocene catalyst, but also to the Lewis acid-base interaction between the metallocene compound and the cocatalyst, where the contribution of the latter was larger than the contribution of the former.
  • Examples 10 through 12 induced severe fouling and had bad particle shapes and an apparent density of 0.1 g/ D or less.
  • the active catalyst is securely fixed to the carrier without being separated from the carrier in slurry polymerization using a solvent such as hexane, etc. and fouling does not occur.
  • the polymer prepared using the supported metallocene catalyst has a good particle shape and a high apparent density.
  • Example 16 in which Compounds A and F were used in the polyethylene polymerization (Example 16) was twice the activity of the supported metallocene catalyst obtained in Example 6 in which Compound F was used in the polyethylene polymerization (Example 14).
  • the polymer obtained in Example 16 had a lower molecular weight and a broader distribution of molecular weight than the polymer obtained in Example 14.
  • the activity of the catalyst can also be controlled and the physical properties and molecular weight distributions of the polymers can be controlled over a wide range. That is, a supported metallocene catalyst which can control the molecular weight distribution in a single reactor can be prepared.

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Abstract

L'invention concerne un catalyseur métallocène sur support qui présente un excellent rendement de support en raison d'une interaction entre un cocatalyseur supporté par un support et un composé métallocène substitué par un groupe fonctionnel pouvant fonctionner comme base de Lewis ainsi qu'une méthode permettant de polymériser une oléfine au moyen du catalyseur métallocène sur support. Dans le catalyseur métallocène sur support, étant donné que le catalyseur métallocène est fortement lié au support par une interaction acide-base de Lewis entre le composé métallocène et le cocatalyseur, le catalyseur métallocène n'est pas séparé du support pendant la polymérisation de la polyoléfine dans une phase boueuse ou gazeuse. Par conséquent, il est possible de prévenir les salissures et le polymère préparé présente une bonne forme des particules et une densité apparente élevée. Par conséquent, le catalyseur métallocène sur support peut être utilisé de façon appropriée dans un procédé classique de polymérisation en phase boueuse ou gazeuse.
PCT/KR2005/002913 2004-09-03 2005-09-02 Catalyseur metallocene sur support, procede de preparation dudit catalyseur et procede de preparation de polyolefine utilisant ledit catalyseur WO2006025709A1 (fr)

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CN2005800020593A CN1910207B (zh) 2004-09-03 2005-09-02 载体茂金属催化剂、制备该催化剂的方法以及使用该催化剂制备聚烯烃的方法
JP2006549157A JP4652343B2 (ja) 2004-09-03 2005-09-02 担持メタロセン触媒、その製造方法及びそれを利用したポリオレフィンの製造方法

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011111980A2 (fr) 2010-03-08 2011-09-15 Lg Chem, Ltd. Catalyseur métallocène supporté, procédé de préparation d'un tel catalyseur métallocène supporté et procédé de préparation de polyoléfine utilisant ceux-ci
EP2545083A2 (fr) * 2010-03-08 2013-01-16 LG Chem, Ltd. Procédé de préparation d'un catalyseur métallocène supporté et procédé de préparation de polyoléfine utilisant ce catalyseur
EP2545084A2 (fr) * 2010-03-08 2013-01-16 LG Chem, Ltd. Catalyseur métallocène supporté, procédé de préparation d'un tel catalyseur métallocène supporté et procédé de préparation de polyoléfine utilisant ceux-ci
EP2545084A4 (fr) * 2010-03-08 2014-01-08 Lg Chemical Ltd Catalyseur métallocène supporté, procédé de préparation d'un tel catalyseur métallocène supporté et procédé de préparation de polyoléfine utilisant ceux-ci
EP2545083A4 (fr) * 2010-03-08 2014-01-08 Lg Chemical Ltd Procédé de préparation d'un catalyseur métallocène supporté et procédé de préparation de polyoléfine utilisant ce catalyseur
US9029486B2 (en) 2010-03-08 2015-05-12 Lg Chem, Ltd. Supported metallocene catalyst, method for preparing the same and method for preparing polyolefin using the same
US9637566B2 (en) 2010-03-08 2017-05-02 Lg Chem, Ltd. Method for preparing supported metallocene catalyst and method for preparing polyolefin using the same
US11078311B2 (en) 2016-10-26 2021-08-03 Exxonmobil Chemical Patents Inc. Single-site catalyst polyolefin polymerization process

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Publication number Publication date
EP1784431A4 (fr) 2009-11-11
CN1910207A (zh) 2007-02-07
CN1910207B (zh) 2013-03-27
TW200613347A (en) 2006-05-01
KR100690345B1 (ko) 2007-03-09
JP4652343B2 (ja) 2011-03-16
JP2007519781A (ja) 2007-07-19
EP1784431A1 (fr) 2007-05-16
US8124557B2 (en) 2012-02-28
EP1784431B1 (fr) 2015-01-07
KR20060021476A (ko) 2006-03-08
US20060052238A1 (en) 2006-03-09
TWI316520B (en) 2009-11-01

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